CN110498915A - A kind of α-carboxyl-ω-hydroxy polyethers are simple, controllable synthesis method - Google Patents
A kind of α-carboxyl-ω-hydroxy polyethers are simple, controllable synthesis method Download PDFInfo
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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Abstract
The invention belongs to technical field of organic synthesis, disclose that a kind of α-carboxyl-ω-hydroxy polyethers are simple, controllable synthesis method.In an inert atmosphere, epoxy monomer is added in hydroxycarboxylic acid esters and no metal Lewis acid-base pair catalyst/initiator system and is reacted, obtain α -ester base-ω-hydroxy polyethers, hydrolyzed, obtain product；The no metal Lewis acid-base pair includes organic base and boron alkyl.The present invention uses the functionalized hydroxy kind initiator of ester group, and wherein hydroxyl causes polymerization, generates the hydroxyl at the end ω, and ester group is then retained in the end α, so that a step obtains the different functional polyethers of both-end.The concerted catalysis of no metal Lewis acid-base pair acts on, and carries out the polymerization reaction of epoxy efficiently at room temperature；The chemo-selective of catalyst system inhibits the side reactions such as transesterification, chain transfer to monomer completely, to can control to obtain α-carboxyl-ω-hydroxy polyethers.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of α-carboxyl-ω-hydroxy polyethers are simple, controllable
Synthetic method.
Background technique
Polyethers is the polymer that backbone structure is mainly made of ehter bond (- C-O-C-), many kinds of, different properties.Wherein
Polyethylene oxide (also known as polyethylene glycol, PEO/PEG) has excellent water solubility and biocompatibility, in daily use chemicals, food, makeup
There is extremely extensive and important purposes in the fields such as product, coating, building, medicine, nanometer.Except abundant object brought by main chain and side group
Outside reason/chemical property, terminal functionality is also the basic source of polyethers performance and purposes.For example, polyethers binary/polyalcohol is raw
Produce polyurethane primary raw material, and polyethers to polyurethane conversion i.e. utilize be terminal hydroxy group reaction.In addition, terminal group functional
The importance of PEG is also significantly embodied in biology and field of medicaments.When polyethylene glycol is as dressing agent, the end group of functionalization become with
The site of other molecules reaction, the PEG with different end group thus can be used as linking arm and carry out different reactions at both ends, make
It is more widely applied.Large biological molecule can be connected to stromal surface by the PEG of this different end group, carry out certain bits to drug
The modification of point, and functionalizing is carried out to nanoparticle, it is used for biological detection or specific identification.
Ester group, carboxyl are classical organo-functional group, can be acted on a variety of reactive groups.Ester group, carboxyl are introduced into polyethers
The end of the chain is the important component in the different functional polyethers research of both-end.Wherein, carboxy-functionalized polyethers can be in temperate condition
Under surface, drug, nanoparticle, biomolecule etc. are chemically modified, and keep being modified the structure and function of object；Carboxyl
The ester bond that modification is formed can be hydrolyzed further, so that the connection of polyethers and drug is broken in vivo by certain speed, released
Drug restores the activity of drug；Carboxyl end group can be further converted to aldehyde radical, amino, dimaleoyl imino, sulfydryl, succinyl
Carbonic ester etc. synthesizes the polyether-modified agent with various active groups.
However, comparing the research of polyether-modified drug and nano material, the synthetic method of such polyethers then develops very late
It is slow.The prior synthesizing method of the different functional polyethers of both-end is terminal groups modification method, i.e., is raw material to its end using the distant pawl polyethers of same end group
Base is modified.Since two functionalizings in end activity is identical, current any reaction method all cannot only transformation wherein one
A end group and retain another.Under normal conditions, the reactant that equivalent is added can only obtain 50% asymmetric polyethers, separately
There is 25% bifunctional polyethers to generate, and retains 25% double hydroxy polyethers.Specific chromatography, ion exchange must be used later
The separation methods such as resin just can get pure asymmetric polyethers.But due to the nature difference very little of three kinds of macromolecule products, divide
It is very big from difficulty, cause separative efficiency poor, yield is extremely low, and product purity is also difficult to ensure.
Another common method is to implement the ring-opening polymerisation of epoxy monomer with specific initiator, and directly synthesis is asymmetric poly-
Ether.Specific initiator is usually the compound containing hydroxyl and another functional group (FG).Wherein hydroxyl causes polymerization, generates the end ω
Hydroxyl, and FG is then retained in the end α, so that a step obtains asymmetric polyethers.The successful implementation of this method requires FG polymerizeing
Absolute inertia is kept in the process, but there must be certain chemical activity that can change after polymerization for further end group
It makes.And epoxy monomer ring-opening polymerisation often uses highly active catalytic/initiation system (such as highly basic), is resistant to strong basicity polymerizing condition
FG and few.Another kind of initiator is the Heterobifunctional alcohol compound containing protecting group, aldehyde radical alcohol, the list protected such as acetal
Glycol, the amino alcohol of benzyl protection etc. of acetal protection.Protecting group is stabilized FG in epoxy monomer polymerization process, polymerization
Changing reaction condition afterwards can deprotection base, release target group (or being deprotected again after ω-hydroxyl transformation).But this side
The non-common compounds of initiator used in method need additional small molecule synthesis step that can obtain, and the remove-insurance of certain functional groups
It protects relatively complicated.
Both the above method is compared it is found that terminal groups modification method can synthesize a variety of polyether-modifieds with different functional groups
Agent, but need more purification lock out operation, high production cost, yield are very low.Special initiation method can a step directly obtain asymmetry
Polyethers, but the functional group that can be generated is limited.Moreover the end group type needed in practical application and combination are ever-changing, it is impossible to be
All different functional polyethers of both-end all develop special initiation and direct synthesis technique, and end group adaptation step is unavoidable after polymerization.But
The premise for smoothly completing end group transformation is first to obtain certain asymmetry PEG, realizes " asymmetryization " of terminal reactive.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the purpose of the present invention is to provide a kind of α-carboxyls-
ω-hydroxy polyethers are simple, controllable synthesis method.The method of the present invention polymerize epoxy monomer using no metal Lewis acid-base pair
High catalytic activity, to the chemical inertness of ester structure, direct synthesis α -ester base-ω-hydroxy polyethers；Ester group is hydrolyzed, by end ester group
It is fully converted into carboxyl end group.Wherein, it is 100% that the monomer conversion of polymerization reaction and the functional group conversions of hydrolysis, which lead,
No side reaction occurs；Gained α-carboxyl-ω-hydroxy polyethers molecular weight and molecular structure can accuracy controllings；Reaction efficiency is high, real
Applying method is easy.
The object of the invention is achieved through the following technical solutions:
A kind of α-carboxyl-ω-hydroxy polyethers are simple, controllable synthesis method, include the following steps:
In an inert atmosphere, hydroxycarboxylic acid esters and no metal Lewis acid-base pair catalyst/initiator system are added in epoxy monomer
Middle reaction obtains α -ester base-ω-hydroxy polyethers, and hydrolysis obtains α-carboxyl-ω-hydroxy polyethers；The no metal Lewis acid-base pair
Including organic base and boron alkyl.
Preferably, the epoxy monomer includes but is not limited to (1) ethylene oxide, (2) straight chained alkyl ethylene oxide (alkyl carbon
Atomicity 1 to 20), (3) straight chained alkyl glycidol ether (atomic number of alkyl carbon 1 to 16), (4) isopropyl glycidyl ether, (5)
Tertiary butyl glycidyl ether, (6) 2- hexyl glycidyl ether, (7) phenyl glycidyl ether, (8) benzyl glycidyl ether,
(9) allyl glycidyl ether, (10) propargyl glycidol ether, (11) glycidyl methacrylate.Concrete structure formula
It is as follows:
Preferably, the hydroxycarboxylic acid esters include but is not limited to (1) 3- hydroxy methyl propionate, the tertiary fourth of (2) 3- hydracrylic acid
Ester, (3) 4 hydroxybutyric acid methyl esters, (4) 5- hydroxyl methyl, (5) 2,2- dimethyl -3- hydroxy methyl propionate, (6) 6- hydroxyl
Ethyl hexanoate, (7) (+)-methyl (S) -3- hydroxyl valerate, (8) (R)-(-)-ethyl 3-hydroxybutanoate, (9) 3-hydroxybutyrate
Ethyl ester, (10) 4- hydroxycyclohexanecarboxylate ethyl ester, (11) 3- hydroxycyclohexanecarboxylate ethyl ester, (12) 3- hydroxyl glutaric acid diformazan
Ester, (13) 3- hydroxyl ethyl glutarate, (14) DL-malic acid diethylester, (15) DL-malic acid dimethyl ester, (16) DL- apple
Sour di-n-butyl, (17) trimethyl citrate, (18) triethyl citrate, (19) tributyl citrate.Concrete structure formula is as follows:
Preferably, the organic base includes but is not limited to various three-level amine (DABCO, PMDETA, ME6TREN,
Sparteine), amidine class (DBN, DBU), guanidine (MTBD, TMG, PMG), triamido phosphine (HMTP, HETP, TMAP, TIPAP) and
Phosphazene base (BEMP, t-BuP1, t-BuP2, EtP2, t-BuP4) etc..Concrete structure formula is as follows:
Preferably, the boron alkyl includes but is not limited to different two ring [3.3.1] nonane (S- of pine pinane base -9- boron of B-
Alphine-Borane), three sec-butyl borine (TsBuB), triisopropyl borine (TiPrB), trimethyl borine (TMB) and its
Its three straight chained alkyl borine (TAB；Carbon chain lengths from 2 to 8).Concrete structure formula is as follows:
Preferably, the reaction carries out in the ontology of epoxy monomer, or in benzene, toluene, tetrahydrofuran, 2- methyl tetrahydro
The in the mixed solvent of one or more of furans, acetone carries out.
Preferably, the concentration of epoxy monomer is 3~15mol/L when the reaction starts.
Preferably, the molar ratio of the boron alkyl and organic base is (0.2~5): 1.
Preferably, the temperature of the reaction be room temperature, the reaction time be 0.5~for 24 hours.
Preferably, the hydrolysis refers to in-situ hydrolysis or fractional hydrolysis；The in-situ hydrolysis process are as follows: after reaction,
Highly basic directly is added into reaction system or strong acid aqueous solution reacts to obtain α-carboxyl-ω-hydroxy polyethers；The fractional hydrolysis
Journey are as follows: after reaction, by α -ester base-ω-hydroxy polyethers precipitating, dry, be dissolved in organic solvent, add highly basic or strong acid
Aqueous solution is hydrolyzed, and obtains α-carboxyl-ω-hydroxy polyethers.
Further, the organic solvent in the hydrolysis is tetrahydrofuran, 2- methyltetrahydrofuran, methylene chloride or third
Ketone.
Further, the temperature of the hydrolysis is 25~60 DEG C, and hydrolysis time is 4~36h.
Synthetic method of the invention have the following advantages that and the utility model has the advantages that
(1) present invention provides a kind of easy, controlledly synthesis α-carboxyl-ω-hydroxy polyethers method.It is functionalized from ester group
Hydroxy compounds sets out, and hydroxyl causes epoxide polymerization, and ester group is retained in the end α；In-situ hydrolysis or fractional hydrolysis, α -ester base is complete
It is converted into α-carboxyl.
(2) due to being difficult to avoid that ester exchange reaction during epoxide polymerization, cause epoxy polymer very with hydroxycarboxylic acid esters
The rare α -ester base-ω-hydroxy polyethers for arriving high yield, and target product isolates and purifies difficulty.Catalytic body provided by the present invention
Selectively high-efficiency polymerization epoxy under the conditions of system can be existing for the ester structure, no transesterification and chain transfer reaction, thus directly
α -ester base-ω-hydroxy polyethers are synthesized, monomer conversion is up to 100%.
(3) catalyst is separated with initiator, utilizes functionalized initiator, directly the synthesis different functional polyethers of both-end；Or
The monomer combination that the initiator of person's polyfunctionality is arranged in pairs or groups different, synthesizes terminal group functional or multiple functionalized, side group is functionalized, is embedding
Sections etc. have the copolymer of various structures feature.
(4) hydroxy compounds is used in combination with dual-component catalyst, solves existing one-component or two-component is organic or have
Epoxy monomer polymerization activity and controllability deficiency, restricted application, catalytic activity are adjusted not under machine metal catalytic initiation system
Enough flexibly, the problems such as metal residual.
(5) catalysis/initiation system high efficiency make the epoxy monomer of relative inertness ring-opening polymerisation can in room temperature, without molten
It is leniently carried out in Conventional glass reactor under conditions of agent or a small amount of solvent (high concentration), lower catalyst amount, and its
Selectivity retain relatively active ester structure can completely during epoxide polymerization.
(6) the different functional polyethers of both-end, but the non-common chemical combination of this kind of initiator can directly be synthesized with specific initiator
Object needs additional small molecule synthesis step that can obtain.The hydroxycarboxylic acid esters that the present invention uses are commercial materials, from a wealth of sources,
To save the mult-step synthetic sequence of functionalized initiators, and additional reactive functional groups are not introduced.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
The conversion ratio of monomer, polymer architecture feature and hydrolysis degree are by Bruker AV400 liquid in following embodiment
Nuclear Magnetic Resonance measures, and solvent is deuterated chloroform.(number-average molecular weight is greater than 4.0kgmol to polyethylene oxide-1When) molecular weight and
Molecular weight dispersity is measured by volume removing chromatogram (SEC), and instrument is using Waters1515 type pump and HR-2, HR-4, HR-6 system
Column chromatographic column, using n,N-Dimethylformamide as mobile phase, 50 DEG C of column temperature, flow velocity 1mL/min；With a series of polyethylene oxide marks
Quasi- sample does calibration curve.The test of the molecular weight and dispersion degree of remaining polymer uses U.S.'s Agilent (Agilent)
The volume removing chromatogram instrument of 1260Infinity model, mobile phase are tetrahydrofuran, 35 DEG C of column temperature, flow velocity 1mL/min；With a system
Column polystyrene or polyethylene oxide standard sample do calibration curve.It is molar part that the number is formulated in following embodiment.
Embodiment 1
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl polyethylene oxide using one pot of two-step method.(1) with monoesters base function
The hydroxy compounds of change is initiator, and no metal Lewis acid-base pair is the ring-opening polymerisation that catalyst implements ethylene oxide (EO)；
(2) basic hydrolysis in situ.Concrete operations are as follows:
(1) 2,2- dimethyl -3- hydroxy methyl propionate, tetrahydrofuran (THF) and EO make after purifying except water process
With.In an inert atmosphere, by 1 part of 2,2- dimethyl -3- hydroxy methyl propionate, 0.1 part of phosphazene base t-BuP1, 0.3 part of three isopropyl
Base borine and appropriate THF are added sequentially to stir evenly in dry glass reactor.Reactor is connected on vacuum line, is arranged
Except bottle inner part gas, and cooled down with ice-water bath.It is steamed at -20 DEG C into 70 parts of dry EO (wherein [EO]0=
12.0mol L-1), seal glass reactor reacts 2h at room temperature.1It is that 100%, SEC is measured slightly that H NMR, which measures EO conversion ratio,
Molecular weight of product is 3.2kg/mol, dispersion degree 1.12.
(2) after polymerization reaction, reaction flask is opened, KOH (3 parts), H are added2The mixed solution of O and THF will react
Bottle is heated to 40 DEG C of reaction 12h.After hydrolysis, it is 2~3 that the HCl solution that 3mol/L is added, which is acidified to reaction solution pH value,
There is solid particle precipitation in reaction flask at this time.With THF dilute reaction solution, neutral alumina and anhydrous MgSO are sequentially added4Stirring,
Filtering.It collects filtrate, is spin-dried for obtain the final product.1It is that 100%, SEC measures crude product molecular weight and is that H NMR, which measures ester group conversion ratio,
3.1kg/mol, dispersion degree 1.13.Hydroxy compounds in catalyst/initiator system described in the present embodiment, organic base and boron alkyl
Molar ratio is 1:0.1:0.3.
Embodiment 2
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl polyethylene oxide using two pots of methods.(1) functionalized with monoesters base
Hydroxy compounds is initiator, and no metal Lewis acid-base pair is the ring-opening polymerisation that catalyst implements ethylene oxide (EO)；(2)
(1) α that step obtains-monoesters base-ω-hydroxyl polyethylene oxide is after precipitating is dry, basic hydrolysis.Concrete operations are as follows:
(1) step epoxide polymerization is the same as embodiment 1.After polymerization reaction, product is collected, it is dry with n-hexane precipitating, vacuum
It is dry to get.α-monoesters base-ω-hydroxyl polyethylene oxide is weighed in clean glass reactor, KOH (3 parts), H are added2O and
Reaction flask is heated to 40 DEG C of reaction 12h by the mixed solution of THF.After hydrolysis, the HCl solution acid of 3mol/L is added
Changing to reaction solution pH value is 2~3, there is solid particle precipitation in reaction flask at this time.With THF dilute reaction solution, anhydrous MgSO is added4
Stirring, filtering.It collects filtrate, is spin-dried for obtain the final product.1It is that 100%, SEC measures crude product molecular weight and is that H NMR, which measures ester group conversion ratio,
3.1kg/mol, dispersion degree 1.13.
Embodiment 3
Change Lewis acid-base pair dosage, 0.01 part of phosphazene base t-BuP is added1With 0.01 part of triisopropyl borine, EO polymerization
Time extends to 7h, remaining is consistent with embodiment 1.After (1) step polymerization reaction,1HNMR measures EO monomer conversion
It is 3.2kg/mol, dispersion degree 1.12 that 100%, SEC, which measure crude product molecular weight,.(2) one-step hydrolysis after reaction,1H
It is that measure crude product molecular weight be 3.0kg/mol, dispersion degree 1.11 to 100%, SEC that NMR, which measures ester group conversion ratio,.The present embodiment
The molar ratio of hydroxy compounds, organic base and boron alkyl is 1:0.01:0.01 in the catalyst/initiator system.
Embodiment 4
Change Lewis acid-base pair dosage, 0.05 part of phosphazene base t-BuP is added1With 0.01 part of triisopropyl borine, EO polymerization
Time extends most 10h, remaining is consistent with embodiment 1.After (1) step polymerization reaction,1H NMR measures the conversion of EO monomer
Rate be 100%, SEC measure crude product molecular weight be 3.2kg/mol, dispersion degree 1.12.(2) one-step hydrolysis after reaction,1It is that measure crude product molecular weight be 3.0kg/mol, dispersion degree 1.11 to 100%, SEC that H NMR, which measures ester group conversion ratio,.This reality
The molar ratio for applying hydroxy compounds, organic base and boron alkyl in the example catalyst/initiator system is 1:0.05:0.01.
Embodiment 5
The concentration of EO polymerization reaction is adjusted to 3mol/L, polymerization time extends to 12h, remaining is consistent with embodiment 1.The
(1) after step polymerization reaction,1It is that measure crude product molecular weight be 3.2kg/ to 100%, SEC that H NMR, which measures EO monomer conversion,
Mol, dispersion degree 1.12.(2) one-step hydrolysis after reaction,1It is that 100%, SEC is measured slightly that H NMR, which measures ester group conversion ratio,
Molecular weight of product is 3.0kg/mol, dispersion degree 1.11.
Embodiment 6
It is toluene by solvent replacement, remaining is consistent with embodiment 1.After (1) step EO polymerize 2h,1H NMR measures EO monomer
Conversion ratio be 100%, SEC measure crude product molecular weight be 3.2kg/mol, dispersion degree 1.12.The reaction of (2) one-step hydrolysis terminates
Afterwards,1It is that measure crude product molecular weight be 3.0kg/mol, dispersion degree 1.11 to 100%, SEC that H NMR, which measures ester group conversion ratio,.
Embodiment 7
It is acetone by solvent replacement, remaining is consistent with embodiment 1.After (1) step EO polymerize 2.5h,1It is mono- that HNMR measures EO
Transformation rate be 100%, SEC measure crude product molecular weight be 3.2kg/mol, dispersion degree 1.12.(2) one-step hydrolysis reaction knot
Shu Hou,1It is that measure crude product molecular weight be 3.0kg/mol, dispersion degree 1.11 to 100%, SEC that H NMR, which measures ester group conversion ratio,.
Embodiment 8
Change initiator into 6 hydroxycaproic acid ethyl ester, remaining is consistent with embodiment 1.After (1) step polymerization reaction,1H
It is that measure crude product molecular weight be 3.2kg/mol, dispersion degree 1.12 to 100%, SEC that NMR, which measures EO conversion ratio,.(2) step water
Solution after reaction,1It is that measure crude product molecular weight be 2.9kg/mol to 100%, SEC that H NMR, which measures ester group conversion ratio, dispersion
Degree is 1.12.
Embodiment 9
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl polypropylene oxide using one pot of two-step method.(1) with monoesters base function
The hydroxy compounds of change is initiator, and no metal Lewis acid-base pair is the ring-opening polymerisation that catalyst implements propylene oxide (PO)；
(2) basic hydrolysis in situ.Concrete operations are as follows:
(1) 6 hydroxycaproic acid ethyl ester, THF and PO are used after purifying except water process.In an inert atmosphere, by 1 part
6 hydroxycaproic acid ethyl ester, 50 parts of PO and appropriate THF are added in dry glass reactor and stir evenly.Continuously add 0.5 part
Phosphazene base t-BuP2With 2.5 parts of boron triethyls (wherein [PO]0=10.0mol/L), 8h is stirred at room temperature.1H NMR measures PO and turns
Rate be 100%, SEC measure crude product molecular weight be 3.0kg/mol, dispersion degree 1.06.
(2) after polymerization reaction, reaction flask is opened, KOH (3 parts), H are added2The mixed solution of O and THF will react
Bottle is heated to 40 DEG C of reaction 12h.After hydrolysis, it is 2~3 that the HCl solution that 3mol/L is added, which is acidified to reaction solution pH value,
There is solid particle precipitation in reaction flask at this time.With THF dilute reaction solution, neutral alumina and anhydrous MgSO are sequentially added4Stirring,
Filtering.It collects filtrate, is spin-dried for obtain the final product.1It is that 100%, SEC measures crude product molecular weight and is that H NMR, which measures ester group conversion ratio,
3.0kg/mol, dispersion degree 1.08.Hydroxy compounds in catalyst/initiator system described in the present embodiment, organic base and boron alkyl
Molar ratio is 1:0.5:2.5.
Embodiment 10
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl polypropylene oxide using two pots of methods.(1) functionalized with monoesters base
Hydroxy compounds is initiator, and no metal Lewis acid-base pair is the ring-opening polymerisation that catalyst implements propylene oxide (PO)；(2)
(1) α that step obtains-monoesters base-ω-hydroxyl polypropylene oxide is after precipitating is dry, basic hydrolysis.Concrete operations are as follows.
(1) step epoxide polymerization is the same as embodiment 9.After polymerization reaction, is terminated and reacted with acetic acid.Dilute reaction solution adds
Enter neutral alumina stirring, filtering.It collects filtrate, is spin-dried for solvent, is dried in vacuo to obtain the final product.By α after purification-monoesters base-ω-hydroxyl
Base polyethylene oxide is placed in clean glass reactor, and KOH (3 parts), H are added2The mixed solution of O and THF, by reaction flask plus
Heat is to 40 DEG C of reaction 12h.After hydrolysis, it is 2~3 that the HCl solution that 3mol/L is added, which is acidified to reaction solution pH value, at this time
There is solid particle precipitation in reaction flask.Anhydrous MgSO is added in reaction solution4Stirring, filtering.It collects filtrate, is spin-dried for obtain the final product.1It is that measure crude product molecular weight be 3.0kg/mol, dispersion degree 1.08 to 100%, SEC that HNMR, which measures ester group conversion ratio,.
Embodiment 11
The present embodiment synthesizes the poly- tertiary butyl glycidyl ether of α-mono carboxylic-ω-hydroxyl using one pot of two-step method.
Epoxy monomer is changed to tertiary butyl glycidyl ether (BGE), remaining is consistent with embodiment 9.(1) step
After BGE reacts 18h at room temperature,1It is that measure crude product molecular weight be 6.8kg/mol to 100%, SEC that H NMR, which measures BGE conversion ratio,
Dispersion degree is 1.08.(2) one-step hydrolysis after reaction,1It is that 100%, SEC measures crude product that H NMR, which measures ester group conversion ratio,
Molecular weight is 6.5kg/mol, dispersion degree 1.12.
Embodiment 12
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl poly allyl glycidylether using one pot of two-step method.
Epoxy monomer is changed to allyl glycidyl ether (AGE), remaining is consistent with embodiment 9.(1) step
After AGE reacts for 24 hours at room temperature,1It is that measure crude product molecular weight be 5.8kg/ to 100%, SEC that H NMR, which measures AGE conversion ratio,
Mol, dispersion degree 1.06.(2) one-step hydrolysis after reaction,1It is that 100%, SEC measures thick production that HNMR, which measures ester group conversion ratio,
Object molecular weight is 5.5kg/mol, dispersion degree 1.11.
Embodiment 13
Change without metal Lewis acid-base pair dosage, 3 parts of phosphazene base t-BuP are added2With 5 parts of triisopropyl borines, AGE gathers
The conjunction time shorten to 18h, remaining is consistent with embodiment 12.After (1) step polymerization reaction,1H NMR measures AGE conversion ratio
Measuring crude product molecular weight for 100%, SEC is 5.9kg/mol, dispersion degree 1.08.(2) one-step hydrolysis after reaction,1H
It is that measure crude product molecular weight be 5.7kg/mol, dispersion degree 1.11 to 100%, SEC that NMR, which measures ester group conversion ratio,.
Embodiment 14
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl polyethylene oxide using one pot of two-step method.(1) with monoesters base function
The hydroxy compounds of change is initiator, and no metal Lewis acid-base pair is the ring-opening polymerisation that catalyst implements ethylene oxide (EO)；
(2) acidic hydrolysis in situ.Concrete operations are as follows.
(1) the 3- hydracrylic acid tert-butyl ester, tetrahydrofuran (THF) and EO are used after purifying except water process.In inertia
In atmosphere, 1 part of 3- hydracrylic acid tert-butyl ester, 0.1 part of ring guanidine MTBD, 0.3 part of three normal-butyl borine and appropriate THF are sequentially added
It is stirred evenly into dry glass reactor.Reactor is connected on vacuum line, excludes bottle inner part gas, and use ice water
Bath cools down.It is steamed at -20 DEG C into 120 parts of dry EO (wherein [EO]0=15.0mol L-1), seal glass reactor in
1h is reacted at room temperature.1It is that measure crude product molecular weight be 5.2kg/mol, dispersion degree to 100%, SEC that H NMR, which measures EO conversion ratio,
It is 1.14.
(2) after polymerization reaction, reaction flask is opened, concentrated hydrochloric acid (5 parts), H are added2The mixed solution of O and THF, will
Reaction flask is heated to 40 DEG C of reaction 8h.After hydrolysis, with THF dilute reaction solution, neutral alumina and nothing are sequentially added
Water MgSO4Stirring, filtering.It collects filtrate, is spin-dried for obtain the final product.1It is that 100%, SEC measures crude product point that HNMR, which measures ester group conversion ratio,
Son amount is 5.0kg/mol, dispersion degree 1.15.Hydroxy compounds, organic base and alkane in catalyst/initiator system described in the present embodiment
The molar ratio of base boron is 1:0.1:0.3.
Embodiment 15
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl polyethylene oxide using two pots of methods.(1) functionalized with monoesters base
Hydroxy compounds is initiator, and no metal Lewis acid-base pair is the ring-opening polymerisation that catalyst implements ethylene oxide (EO)；(2)
(1) α that step obtains-mono carboxylic-ω-hydroxyl polyethylene oxide is after precipitating is dry, acidic hydrolysis.Concrete operations are as follows.
(1) step epoxide polymerization is the same as embodiment 14.After polymerization reaction, product is collected, it is dry with n-hexane precipitating, vacuum
It is dry to get.α-monoesters base-ω-hydroxyl polyethylene oxide is weighed in clean glass reactor, addition concentrated hydrochloric acid (5 parts),
H2Reaction flask is heated to 40 DEG C of reaction 8h by the mixed solution of O and THF.After hydrolysis, with THF dilute reaction solution, according to
Secondary addition neutral alumina and anhydrous MgSO4Stirring, filtering.It collects filtrate, is spin-dried for obtain the final product.1H NMR measures ester group conversion ratio
It is 5.0kg/mol, dispersion degree 1.13 that 100%, SEC, which measure crude product molecular weight,.
Embodiment 16
Organic base is changed to tertiary amine DABCO, remaining is consistent with embodiment 14.(1) step EO polymerize 2h,1H NMR is surveyed
EO conversion ratio is that measure crude product molecular weight be 5.2kg/mol, dispersion degree 1.09 to 100%, SEC.The reaction of (2) one-step hydrolysis
After 12h,1It is that measure crude product molecular weight be 5.1kg/mol to 100%, SEC that H NMR, which measures ester group conversion ratio, and dispersion degree is
1.09。
Embodiment 17
Organic base is changed to triamido phosphine HMTP, remaining is consistent with embodiment 14.(1) step EO polymerize 5h,1H NMR
Measuring EO conversion ratio is that measure crude product molecular weight be 5.2kg/mol, dispersion degree 1.09 to 100%, SEC.(2) one-step hydrolysis is anti-
After answering 12h,1It is that measure crude product molecular weight be 5.0kg/mol to 100%, SEC that H NMR, which measures ester group conversion ratio, and dispersion degree is
1.10。
Embodiment 18
Epoxy monomer is changed to PO, remaining is consistent with embodiment 14.(1) step PO polymerize 12h,1H NMR measures PO and turns
Rate be 100%, SEC measure crude product molecular weight be 7.2kg/mol, dispersion degree 1.05.After (2) one-step hydrolysis reacts 12h
,1It is that measure crude product molecular weight be 7.0kg/mol, dispersion degree 1.08 to 100%, SEC that H NMR, which measures ester group conversion ratio,.
Embodiment 19
The present embodiment synthesizes α-dicarboxyl-ω-hydroxyl polyethylene oxide using one pot of two-step method.
Initiator is changed to 3- hydroxyl dimethyl glutarate, remaining is consistent with embodiment 1.The polymerization of (1) step is anti-
After answering,1It is that measure crude product molecular weight be 3.3kg/mol to 100%, SEC that H NMR, which measures EO conversion ratio, and dispersion degree is
1.12.(2) one-step hydrolysis after reaction,1It is that 100%, SEC measures crude product molecular weight and is that H NMR, which measures ester group conversion ratio,
3.0kg/mol, dispersion degree 1.12.
Embodiment 20
The present embodiment synthesizes α-dicarboxyl-ω-hydroxyl polyethylene oxide using one pot of two-step method.
Initiator is changed to DL-malic acid diethylester, remaining is consistent with embodiment 1.(1) step polymerization reaction knot
Shu Hou,1It is that measure crude product molecular weight be 3.3kg/mol, dispersion degree 1.12 to 100%, SEC that H NMR, which measures EO conversion ratio,.The
(2) one-step hydrolysis after reaction,1It is that measure crude product molecular weight be 3.0kg/ to 100%, SEC that H NMR, which measures ester group conversion ratio,
Mol, dispersion degree 1.12.
Embodiment 21
The present embodiment synthesizes α-dicarboxyl-ω-hydroxyl polypropylene oxide using one pot of two-step method.
Initiator is changed to 3- hydroxyl dimethyl glutarate, remaining is consistent with embodiment 9.The polymerization of (1) step is anti-
After answering,1It is that measure crude product molecular weight be 3.2kg/mol to 100%, SEC that H NMR, which measures PO conversion ratio, and dispersion degree is
1.08.(2) one-step hydrolysis after reaction,1It is that 100%, SEC measures crude product molecular weight and is that H NMR, which measures ester group conversion ratio,
3.0kg/mol, dispersion degree 1.08.
Embodiment 22
The present embodiment synthesizes α-three carboxyl-ω-hydroxyl polyethylene oxide using one pot of two-step method.
Initiator is changed to triethyl citrate, remaining is consistent with embodiment 1.(1) step polymerization reaction terminates
Afterwards,1It is that measure crude product molecular weight be 3.1kg/mol, dispersion degree 1.10 to 100%, SEC that H NMR, which measures EO conversion ratio,.The
(2) one-step hydrolysis after reaction,1It is that measure crude product molecular weight be 3.0kg/ to 100%, SEC that H NMR, which measures ester group conversion ratio,
Mol, dispersion degree 1.11.
Embodiment 23
The present embodiment synthesizes α-three carboxyl-ω-hydroxyl polypropylene oxide using one pot of two-step method.
Initiator is changed to triethyl citrate, remaining is consistent with embodiment 9.(1) step polymerization reaction terminates
Afterwards,1It is that measure crude product molecular weight be 3.2kg/mol, dispersion degree 1.08 to 100%, SEC that H NMR, which measures PO conversion ratio,.The
(2) one-step hydrolysis after reaction,1It is that measure crude product molecular weight be 3.0kg/ to 100%, SEC that H NMR, which measures ester group conversion ratio,
Mol, dispersion degree 1.08.
Embodiment 24
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl (epoxy ethane-epoxy propane) random copolymerization using one pot of two-step method
Object.(1) using the functionalized hydroxy compounds of monoesters base as initiator, no metal Lewis acid-base pair is that catalyst implements epoxy second
The random copolymerization of alkane (EO) and propylene oxide (PO)；(2) basic hydrolysis in situ.Concrete operations are as follows:
(1) 2,2- dimethyl -3- hydroxy methyl propionate, tetrahydrofuran (THF), EO and PO are after purifying except water process
It uses.In an inert atmosphere, by 1 part of 2,2- dimethyl -3- hydroxy methyl propionate, 50 parts of PO, 0.15 part of three normal-butyl borine and
Appropriate THF is added sequentially to stir evenly in dry glass reactor.Reactor is connected on vacuum line, is excluded inside bottle
Divide gas, and is cooled down with ice-water bath.It is steamed at -20 DEG C into 70 parts of dry EO (wherein [EO]0=7.4mol L-1,
[PO]0=5.3mol L-1), it stirs evenly.At 0 DEG C, nitrogen stream protection is lower to be added 0.05 part of phosphazene base t-BuP1, seal glass
Reactor reacts 15h at room temperature.1It is 100%, PO conversion ratio is that 100%, SEC measures crude product that H NMR, which measures EO conversion ratio,
Molecular weight is 4.8kg/mol, dispersion degree 1.16.
(2) after polymerization reaction, reaction flask is opened, KOH (3 parts), H are added2The mixed solution of O and THF will react
Bottle is heated to 40 DEG C of reaction 6h.After hydrolysis, it is 2~3 that the HCl solution that 3mol/L is added, which is acidified to reaction solution pH value,
There is solid particle precipitation in reaction flask at this time.With THF dilute reaction solution, neutral alumina and anhydrous MgSO are sequentially added4Stirring,
Filtering.It collects filtrate, is spin-dried for obtain the final product.1It is that 100%, SEC measures crude product molecular weight and is that H NMR, which measures ester group conversion ratio,
4.5kg/mol, dispersion degree 1.18.Hydroxy compounds in catalyst/initiator system described in the present embodiment, organic base and boron alkyl
Molar ratio is 1:0.05:0.15.
Embodiment 25
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl polyethylene oxide-b- propyleneoxides using one pot of two-step method
Copolymer.(1) using the functionalized hydroxy compounds of monoesters base as initiator, no metal Lewis acid-base pair is that catalyst implements ring
The continuous polymerization of oxidative ethane (EO) and propylene oxide (PO)；(2) basic hydrolysis in situ.Concrete operations are as follows:
(1) 2,2- dimethyl -3- hydroxy methyl propionate, tetrahydrofuran (THF), EO and PO are after purifying except water process
It uses.In an inert atmosphere, by 1 part of 2,2- dimethyl -3- hydroxy methyl propionate, 0.05 part of phosphazene base t-BuP1, 0.15 part three
Normal-butyl borine and appropriate THF are added sequentially to stir evenly in dry glass reactor.Reactor is connected to vacuum line
On, bottle inner part gas is excluded, and cooled down with ice-water bath.It is steamed at -20 DEG C into 70 parts of dry EO (wherein [EO]0=
11.7mol L-1), seal glass reactor reacts 1.5h at room temperature.1It is that 100%, SEC is measured that H NMR, which measures EO conversion ratio,
Crude product molecular weight is 3.1kg/mol, dispersion degree 1.10.Reaction flask is moved into glove box, 50 parts of PO are added (wherein
[PO]0=5.3mol L-1).Heating reaction flask to reaction solution be it is homogeneous, reaction flask is slowly cooled to room temperature, and continue to stir
12h。1It is that measure crude product molecular weight be 4.6kg/mol, dispersion degree 1.12 to 100%, SEC that H NMR, which measures PO conversion ratio,.
(2) after polymerization reaction, reaction flask is opened, KOH (3 parts), H are added2The mixed solution of O and THF, sealing are anti-
Bottle is answered to react 36h at room temperature.After hydrolysis, it is 2~3 that the HCl solution that 3mol/L is added, which is acidified to reaction solution pH value,
There is solid particle precipitation in reaction flask at this time.With THF dilute reaction solution, neutral alumina and anhydrous MgSO are sequentially added4Stirring,
Filtering.It collects filtrate, is spin-dried for obtain the final product.1It is that 100%, SEC measures crude product molecular weight and is that H NMR, which measures ester group conversion ratio,
4.5kg/mol, dispersion degree 1.11.Hydroxy compounds in catalyst/initiator system described in the present embodiment, organic base and boron alkyl
Molar ratio is 1:0.05:0.15.
Embodiment 26
The present embodiment synthesizes α-mono carboxylic-ω-hydroxyl polypropylene oxide-b- poly-ethylene oxide block using one pot of two-step method
Copolymer.(1) using the functionalized hydroxy compounds of monoesters base as initiator, no metal Lewis acid-base pair is that catalyst implements ring
The continuous polymerization of Ethylene Oxide (PO) and ethylene oxide (EO)；(2) basic hydrolysis in situ.Concrete operations are as follows:
(1) 2,2- dimethyl -3- hydroxy methyl propionate, tetrahydrofuran (THF), EO and PO are after purifying except water process
It uses.In an inert atmosphere, by 1 part of 2,2- dimethyl -3- hydroxy methyl propionate, 0.05 part of phosphazene base t-BuP1, 0.15 part three
Normal-butyl borine, 50 parts of PO and appropriate THF are added sequentially in dry glass reactor (wherein [PO]0=8.3mol L-1),
7h is stirred at room temperature.1It is that measure crude product molecular weight be 3.5kg/mol to 100%, SEC that H NMR, which measures PO conversion ratio, dispersion
Degree is 1.04.Reactor is connected on vacuum line, excludes bottle inner part gas, and cooled down with ice-water bath.At -20 DEG C
It steams into 70 parts of dry EO (wherein [EO]0=7.4mol L-1), seal glass reactor reacts 3h at room temperature.1HNMR is measured
EO conversion ratio is that measure crude product molecular weight be 4.8kg/mol, dispersion degree 1.10 to 100%, SEC.
(2) after polymerization reaction, reaction flask is opened, KOH (3 parts), H are added2The mixed solution of O and THF will react
Bottle is heated to 60 DEG C of reaction 4h.After hydrolysis, it is 2~3 that the HCl solution that 3mol/L is added, which is acidified to reaction solution pH value,
There is solid particle precipitation in reaction flask at this time.With THF dilute reaction solution, neutral alumina and anhydrous MgSO are sequentially added4Stirring,
Filtering.It collects filtrate, is spin-dried for obtain the final product.1It is that 100%, SEC measures crude product molecular weight and is that H NMR, which measures ester group conversion ratio,
4.6kg/mol, dispersion degree 1.11.Hydroxy compounds in catalyst/initiator system described in the present embodiment, organic base and boron alkyl
Molar ratio is 1:0.05:0.15.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of α-carboxyl-ω-hydroxy polyethers are simple, controllable synthesis method, it is characterised in that include the following steps:
In an inert atmosphere, by epoxy monomer be added hydroxycarboxylic acid esters in no metal Lewis acid-base pair catalyst/initiator system instead
It answers, obtains α -ester base-ω-hydroxy polyethers, hydrolyze, obtain α-carboxyl-ω-hydroxy polyethers；The no metal Lewis acid-base pair includes
Organic base and boron alkyl.
2. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
In: the epoxy monomer includes straight chained alkyl ethylene oxide, the alkyl carbon atoms of ethylene oxide, atomic number of alkyl carbon for 1~20
Number is 1~16 straight chained alkyl glycidol ether, isopropyl glycidyl ether, tertiary butyl glycidyl ether, 2- ethylhexyl contract
Water glycerin ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidol ether or first
Base glycidyl acrylate.
3. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
In: the hydroxycarboxylic acid esters include 3- hydroxy methyl propionate, the 3- hydracrylic acid tert-butyl ester, 4 hydroxybutyric acid methyl esters, 5- hydroxyl penta
Sour methyl esters, 2,2- dimethyl -3- hydroxy methyl propionate, 6 hydroxycaproic acid ethyl ester, (+)-methyl (S) -3- hydroxyl valerate, (R) -
(-)-ethyl 3-hydroxybutanoate, ethyl 3-hydroxybutanoate, 4- hydroxycyclohexanecarboxylate ethyl ester, 3- hydroxycyclohexanecarboxylate ethyl ester,
3- hydroxyl dimethyl glutarate, 3- hydroxyl ethyl glutarate, DL-malic acid diethylester, DL-malic acid dimethyl ester, DL- apple
Sour di-n-butyl, trimethyl citrate, triethyl citrate or tributyl citrate.
4. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
In: the organic base includes DABCO, PMDETA, ME6TREN, sparteine, DBN, DBU, MTBD, TMG, PMG, HMTP,
HETP, TMAP, TIPAP, BEMP, t-BuP1, t-BuP2, EtP2Or t-BuP4；The boron alkyl includes the different loose pinane base -9- boron of B-
Three straight chains that two rings [3.3.1] nonane, three sec-butyl borines, triisopropyl borine, trimethyl borine or carbon chain lengths are 2~8
Alkyl borane.
5. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
In: the reaction carries out in the ontology of epoxy monomer, or in benzene, toluene, tetrahydrofuran, 2- methyltetrahydrofuran, acetone
One or more kinds of in the mixed solvents carry out.
6. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
In: the concentration of epoxy monomer is 3~15mol/L when the reaction starts.
7. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
In: the molar ratio of the boron alkyl and organic base is (0.2~5): 1.
8. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
It is room temperature in: the temperature of the reaction, the reaction time is 0.5~for 24 hours.
9. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
In: the hydrolysis refers to in-situ hydrolysis or fractional hydrolysis；The in-situ hydrolysis process are as follows: after reaction, directly toward reactant
Highly basic is added in system or strong acid aqueous solution reacts to obtain α-carboxyl-ω-hydroxy polyethers；The fractional hydrolysis process are as follows: reaction knot
α -ester base-ω-hydroxy polyethers precipitating, drying is dissolved in organic solvent by Shu Hou, and the aqueous solution for adding highly basic or strong acid carries out
Hydrolysis, obtains α-carboxyl-ω-hydroxy polyethers；The organic solvent is tetrahydrofuran, 2- methyltetrahydrofuran, methylene chloride or third
Ketone.
10. a kind of α-carboxyl-ω-hydroxy polyethers according to claim 1 are simple, controllable synthesis method, feature exists
In: the temperature of the hydrolysis is 25~60 DEG C, and hydrolysis time is 4~36h.
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